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WO1988010260A1 - ''meso-lactide'' et son procede de preparation - Google Patents

''meso-lactide'' et son procede de preparation Download PDF

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Publication number
WO1988010260A1
WO1988010260A1 PCT/EP1988/000531 EP8800531W WO8810260A1 WO 1988010260 A1 WO1988010260 A1 WO 1988010260A1 EP 8800531 W EP8800531 W EP 8800531W WO 8810260 A1 WO8810260 A1 WO 8810260A1
Authority
WO
WIPO (PCT)
Prior art keywords
lactide
meso
group
carbon atoms
tin
Prior art date
Application number
PCT/EP1988/000531
Other languages
German (de)
English (en)
Inventor
Manfred Müller
Joachim Hess
Wilhelm-Gustav Schnell
Dieter Bendix
Günther ENTENMANN
Original Assignee
Boehringer Ingelheim Kg
Boehringer Ingelheim International Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Boehringer Ingelheim Kg, Boehringer Ingelheim International Gmbh filed Critical Boehringer Ingelheim Kg
Priority to AT88905758T priority Critical patent/ATE73793T1/de
Publication of WO1988010260A1 publication Critical patent/WO1988010260A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/64—Use of materials characterised by their function or physical properties specially adapted to be resorbable inside the body
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
    • A61L17/06—At least partially resorbable materials
    • A61L17/10—At least partially resorbable materials containing macromolecular materials
    • A61L17/12—Homopolymers or copolymers of glycolic acid or lactic acid
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04—Macromolecular materials
    • A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
    • C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides

Definitions

  • the invention relates to meso-lactide, processes for its preparation and its use for the production of polymers and copolymers.
  • Lactic acid-based polymers are of primary interest for use in surgery and wound care because these polymers are broken down in the body into natural metabolic products.
  • biodegradable polymers and copolymers are sufficiently known from the prior art and do not need to be explained in detail.
  • the use of degradable polymers avoids the second operations to remove the implant that were previously necessary when using metal implants. Since it has been known that the composition and production (polymerization conditions, polymerization rate) of the polymers have a significant influence on the stability (tensile and flexural strength) and the rate of degradation of the polymers, there has been great interest in optically pure, well-defined monomers. In the case of lactides, the corresponding dimeric cyclic esters are used as "monomers".
  • the cyclic diester of lactic acid I is referred to as meso-lactide
  • the object is achieved in that a mixture of D, L-lactide and meso-lactide is rectified under reduced pressure. After recrystallization, a pure meso-lactide with a melting point of 52.8 ° C. is obtained from the first distillate.
  • Racemic polylactic acid (50: 50 / D: L) is derived in the presence of a suitable catalyst, for example in the presence of 0.05 to 1.0% by weight of tin dust, Sn 2+ salts or an organic tin compound a carboxylic acid with up to 20 carbon atoms heated to 130 to 230 ° C. under reduced pressure, the lactide which forms is distilled off and polylactic acid is added continuously or batchwise.
  • a suitable catalyst for example in the presence of 0.05 to 1.0% by weight of tin dust, Sn 2+ salts or an organic tin compound a carboxylic acid with up to 20 carbon atoms heated to 130 to 230 ° C. under reduced pressure, the lactide which forms is distilled off and polylactic acid is added continuously or batchwise.
  • Tin compounds which are particularly suitable as catalysts are compounds of the general structure
  • X represents a branched or unbranched alkyl or alkenyl radical having up to 19 carbon atoms or a naphthyl radical, or compounds of the general structure
  • Y represents a branched or unbranched alkylene or alkenylene radical having up to 18 carbon atoms or a phenyl radical.
  • Preferred catalysts are tin tartrate, tin oxalate, tin dicaprylate, tin dilaurate, tin dipalmitate, tin distearate, tin dioleate (derivative of oleic acid), tin ⁇ -naphthoeate or tin ⁇ -naphthoeate.
  • Tin dioctoate better known as tin di (2-ethylhexanoate), or tin dust is particularly preferred.
  • the racemic polylactic acid used in the process can be prepared in a separate reaction step by known processes by dewatering racemic lactic acid.
  • lactic acid is used instead of the polylactic acid.
  • the lactic acid is dewatered in the presence of the catalyst at reduced pressure with increasing temperature. Dewatering generally takes place at pressures of about 10 to 50 hPa, the temperature in the reactor rising to about 150 to 170 ° C.
  • an average molecular weight of the polylactic acid thus formed of about 400 to 2000, preferably 600-800, is reached, lactide is continuously distilled off and then polylactic acid is added continuously or batchwise.
  • lactic acid can also be drawn into the continuous process instead of polylactic acid.
  • racemic polylactic acid is introduced and 0.05 to 1.0% by weight, preferably 0.1 to 0.8% by weight of tin dust or the organotin compound is added.
  • the mixture is then heated to 130 to 230 ° C., preferably 180 to 200 ° C., under reduced pressure, the crude lactide formed, ie a mixture of D, L-lactide and meso-lactide, being distilled off.
  • the optimal temperature range depends on the vacuum applied and can be determined by simple tests. The lowest possible distillation temperature has a favorable effect on the purity of the distillate.
  • racemic polylactic acid is refilled. This is conveniently done in molten form. Refilling can be done batchwise (in portions) or in continuous form, for example by pumping. The replenished amount may well be larger than the original amount used at the start of the reaction.
  • the remaining volume of the reactor contents is not critical in a wide range with regard to the quality of the product, but it is advisable to fill up after about 50 to 90% conversion. It cannot be ruled out that an excessive lowering of the reactor contents leads to a deterioration in the product.
  • the feed is expediently such that the volume of the reactor contents is kept largely constant.
  • racemic lactic acid is used directly in the reactor instead of racemic polylactic acid
  • dehydration of the lactic acid to polylactic acid up to an average molecular weight of about 400-2000 preferably takes place before depolymerization to the crude lactide in the presence of the catalyst of the organotin compound or the tin dust 500 to 800.
  • the dewatering is preferably carried out at about 30 hPa with increasing temperature up to about 170 ° C. After the desired molecular weight has been reached, the batch is processed further as described above.
  • racemic lactic acid can also be added in a further process variant, water being then first distilled off from the reaction mixture until the desired molecular weight of the polylactic acid is obtained. The further procedure then takes place as described above.
  • the use or replenishment of lactic acid instead of polylactic acid has no disadvantages in terms of yield compared to the variants described above. It is advantageous that the reaction time for dewatering the lactic acid is shortened by approximately 50%. The molecular weight of the resulting polylactic acid is determined by titration of the end groups.
  • the crude lactide distilled off which consists of a mixture of meso- and D, L-lactide, is then first of all from a C 1 to C 4 alcohol (such as, for example, methanol, ethanol, n-propanol, isopropanol), preferably isopropanol, like.
  • the crystals obtained therefrom, which consist of a mixture of meso- and D, L-lactide, are then first recrystallized from a C 1 to C 4 alcohol (such as, for example, methanol, ethanol, n-propanol, isopropanol), preferably isopropanol .
  • This second crystallizate thus obtained is then dissolved in a halogenated hydrocarbon, preferably chloroform, particularly preferably 1,2-dichloroethane, or an aliphatic ether, preferably diethyl ether, with D, L-lactide then being crystallized out.
  • a halogenated hydrocarbon preferably chloroform, particularly preferably 1,2-dichloroethane, or an aliphatic ether, preferably diethyl ether, with D, L-lactide then being crystallized out.
  • the remaining mother liquor consisting of a mixture of meso-lactide and D, L-lactide, in a ratio of about 60:40, is concentrated and the residue is rectified according to the invention for further separation.
  • the meso-lactide according to the invention is obtained from the first distillate. If necessary, this can be recrystallized for further purification.
  • Preferred solvents are C 1 -C 4 alcohols, preferably isopropanol, or to
  • the main purpose of this recrystallization is to remove the free acid formed to a small extent in the distillation. It is self-evident that a preliminary run is discarded before the desired first distillate from meso-lactide.
  • the lead generally consists of solvent residues resulting from the evaporation of the mother liquor and possibly from small amounts of reaction products from the solvent and the lactide, such as the isopropyl ester, if isopropanol was used as the solvent.
  • the rectification can be carried out using distillation columns which correspond to the prior art and have a certain minimum separation capacity (number of plates, variable reflux ratio). A theoretical minimum number of trays, which is required for the separation of two or more components, generally results from the boiling point difference of the components to be separated.
  • the boiling points differ from pure meso-lactide and D, L-lactide in a wide pressure range of approx. 7 ° C.
  • the relationship between the theoretical plate number and the actual separation performance, the practical plate number, of a column depends on many factors, but can be determined by simple experiments. If this minimum number of trays is not reached by the equipment used, repeated distillation is necessary.
  • the meso-lactide produced by the process according to the invention is characterized by the following physical parameters. Melting point 52.77 ° C determined by the DTA method
  • the meso-lactide according to the invention is particularly suitable for the production of defined polymers and copolymers.
  • this relates in particular to a poly (meso-lactide) produced from the “pure” monomer according to the invention, and also to a copolymer prepared by polymerizing meso-lactide using the monomers mentioned below.
  • Suitable for this are 1,3-dioxan-2-ones of structure II, 1,4-dioxan-2-ones of structure III, lactides of structure IV and lactones of structure V
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 can be the same or different and hydrogen, a branched or unbranched
  • Amino group an alkylamino, dialkylamino or quaternary amino group with preferably 1 to 4
  • Cycloalkyl group with 3 to 6 carbon atoms which can be substituted like an alkyl group, one
  • Alkoxycarbonyl group having 1 to 5 carbon atoms in the alkoxy group an optionally substituted one
  • Halogen is an atom from the group fluorine
  • Chlorine, bromine or iodine understood, preferred
  • alkyl groups are
  • butyl, preferred aryl groups are phenyl or substituted phenyl. It is assumed that
  • Residues of the same carbon atoms should be selected so that the preparation of the compounds of the general
  • Preferred monomers are:
  • Trimethylene carbonate and 1,4-dioxanone Trimethylene carbonate and 1,4-dioxanone.
  • the ratio of the monomers can be chosen in a wide range between 1 to 99 to 99 to 1 mol% (meso-lactide: monomer).
  • Preferred copolymers are:
  • the polymesolactide according to the invention has a purely syndiotactic structure.
  • the polymers produced according to the invention can be used, for example, for the production of sutures, active substance carriers, surgical implants - plates, screws and pins for fixing bone elements - prostheses and filling materials - nets and foils for soft tissue reconstruction - foils, foamed foils and powders for wound treatment.
  • the polymers and copolymers claimed according to the invention can be prepared from the monomers described in analogy to known processes. This includes processes that are carried out in the melt, in solution or in suspension.
  • Suitable polymerization catalysts are, for example, organic tin compounds - preferably tin octoate (tin di (2-ethylhexanoate) and tin salts such as tin (II) chloride.
  • the reaction time of the polyraerization is between one and 72 hours; the reaction temperature between 100 and 180 ° C.
  • Tin-d ⁇ ) salt (tin dioctoate) are added and the mixture is heated to 194 ° -198 ° C. under a vacuum of 33-17 hPa.
  • D L-lactide and meso-lactide distill off.
  • 270 kg of the polylactic acid described above are drawn in and 252 kg of lactide are obtained under the aforementioned conditions.
  • the crystals contain only D, L-lactide and are practically free of meso-lactide.
  • Tin (II) octate as catalyst for 72 hours at 105 ° C in
  • the polymers obtained are characterized by determining the inherent viscosity (I.V.) in chloroform at 25 ° C. in a concentration of 0.1 g / dl:
  • the polymers obtained are characterized by determining the inherent viscosity in chloroform at 25 ° C. in a concentration of 0.1 g / dl:
  • the polymers obtained are characterized by determining the inherent viscosity in chloroform and dioxane at 25 ° C. and in hexafluoroisopropanol (HF IP) at 30 ° each in a concentration of 0.1 g / d1:
  • the polymer block obtained is characterized by determining the inherent viscosity in chloroform at 25 ° C. in a concentration of 0.1 g / dl:
  • the residual monomer content determined by a 400 MHz 1H-NMR, measured in deuterochloroform, is 1.7% by weight.
  • the spectrum also shows a syndiotactic structure of the polymer.
  • the material has a bending strength of> 140 N / mm 2 .
  • Tin (II) octoate as a catalyst at 160 ° C between 1 and
  • copolymers obtained are characterized by determining the inherent viscosity in chloroform and dioxane at 25 ° C. and in hexafluoroisoproanol (HFIP) at 30 ° C. each in a concentration of 0.1 g / dl:
  • the copolymers obtained were characterized by determining the inherent viscosity in chloroform and dioxane at 25 ° C. and in hexafluoroisopropanol (HFIP) at 30 ° C. in each case in a concentration of 0.1 g / dl: Time I .V. (CHCl 3 ) (dioxane) (HFIP) [h] [dl / g] [dl / g] [dl / g] [dl / g]

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Vascular Medicine (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Surgery (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Inorganic Chemistry (AREA)
  • Dermatology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Hematology (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
  • Materials For Medical Uses (AREA)

Abstract

Méso-lactide dont le point de fusion s'élève à 52,8°C, son procédé de préparation et son utilisation lors de la fabrication de polymères et de copolymères résorbables.
PCT/EP1988/000531 1987-06-16 1988-06-15 ''meso-lactide'' et son procede de preparation WO1988010260A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88905758T ATE73793T1 (de) 1987-06-16 1988-06-15 Meso-lactid und verfahren zu seiner herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP3720060.7 1987-06-16
DE3720060 1987-06-16

Publications (1)

Publication Number Publication Date
WO1988010260A1 true WO1988010260A1 (fr) 1988-12-29

Family

ID=6329807

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1988/000531 WO1988010260A1 (fr) 1987-06-16 1988-06-15 ''meso-lactide'' et son procede de preparation

Country Status (5)

Country Link
US (1) US4983745A (fr)
EP (1) EP0318567B1 (fr)
JP (1) JPH02500593A (fr)
DE (1) DE3869343D1 (fr)
WO (1) WO1988010260A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0427185A2 (fr) * 1989-11-09 1991-05-15 Boehringer Ingelheim Kg Copolymères de carbonate de triméthylène et de lactides optiquement inactives
WO1994008078A1 (fr) * 1992-10-02 1994-04-14 Cargill, Incorporated Tissus de lactide polymere stables en fusion et procede de fabrication
EP0592911A1 (fr) * 1992-10-14 1994-04-20 BASF Aktiengesellschaft Procédé pour la fabrication par injection et moussage d'objets en polylactide à haute résistance et haute rigidité
WO1995009879A1 (fr) * 1993-10-07 1995-04-13 Cargill, Incorporated Procede pour la production continue de lactide et de polymeres de lactide
WO1998007458A1 (fr) * 1996-08-19 1998-02-26 Korea Institute Of Science And Technology Methode de revetement de surfaces destinees aux implants metalliques
EP0893462A3 (fr) * 1992-01-24 1999-10-20 Cargill, Incorporated Procédé continu pour la préparation de lactide et polylactides
WO2010022966A2 (fr) * 2008-08-29 2010-03-04 Uhde Inventa-Fischer Gmbh Procédé servant à préparer un mélange de dérivés de lactide
DE102013011399A1 (de) 2012-07-31 2014-02-06 Amw Gmbh Implantat mit Risperidon
EP2876124A1 (fr) 2013-11-20 2015-05-27 Uhde Inventa-Fischer GmbH Procédé et dispositif de fabrication d'un mélange d'acide polylactique et mélange d'acide polylactique

Families Citing this family (39)

* Cited by examiner, † Cited by third party
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JP2725870B2 (ja) * 1988-08-08 1998-03-11 バイオパック テクノロジー，リミテッド 分解可能なラクチド熱可塑性プラスチック
US5149833A (en) * 1989-05-26 1992-09-22 Boehringer Ingelheim Gmbh Process for preparing D,L-Lactide
DE4018371A1 (de) * 1989-06-09 1990-12-13 Boehringer Ingelheim Kg Resorbierbare formkoerper und verfahren zu ihrer herstellung
DE3936191C2 (de) * 1989-10-31 1996-10-17 Boehringer Ingelheim Kg Neue Copolymere aus Milchsäure und Weinsäure, ihre Herstellung sowie ihre Verwendung
US5091544A (en) * 1990-05-08 1992-02-25 E. I. Du Pont De Nemours And Company Process for rapid conversion of oligomers to cyclic esters
US5080665A (en) * 1990-07-06 1992-01-14 American Cyanamid Company Deformable, absorbable surgical device
AU8283391A (en) * 1990-07-13 1992-02-04 E.I. Du Pont De Nemours And Company High yield recycle process for lactide
US5076983A (en) * 1990-07-16 1991-12-31 E. I. Du Pont De Nemours And Company Polyhydroxy acid films
US6353030B1 (en) * 1990-08-01 2002-03-05 Novartis Ag Relating to organic compounds
US5117008A (en) * 1990-10-23 1992-05-26 E. I. Du Pont De Nemours And Company Solvent scrubbing recovery of lactide and other dimeric cyclic esters
US5089632A (en) * 1991-01-30 1992-02-18 E. I. Du Pont De Nemours And Company Process for preparing cyclic esters using a fluorocarbon
US5142023A (en) * 1992-01-24 1992-08-25 Cargill, Incorporated Continuous process for manufacture of lactide polymers with controlled optical purity
US6005067A (en) 1992-01-24 1999-12-21 Cargill Incorporated Continuous process for manufacture of lactide polymers with controlled optical purity
US5247058A (en) * 1992-01-24 1993-09-21 Cargill, Incorporated Continuous process for manufacture of lactide polymers with controlled optical purity
US5258488A (en) * 1992-01-24 1993-11-02 Cargill, Incorporated Continuous process for manufacture of lactide polymers with controlled optical purity
US5247059A (en) * 1992-01-24 1993-09-21 Cargill, Incorporated Continuous process for the manufacture of a purified lactide from esters of lactic acid
US5236560A (en) * 1992-03-13 1993-08-17 E. I. Du Pont De Nemours And Company Solventless dimeric cyclic ester distillation process
US5357034A (en) * 1992-09-08 1994-10-18 Camelot Technologies Inc. Lactide polymerization
BR9305658A (pt) * 1992-10-02 1996-11-26 Cargill Inc Papel tendo um polímero de lactideo estável em fusao e processo para sua produçao
US6005068A (en) 1992-10-02 1999-12-21 Cargill Incorporated Melt-stable amorphous lactide polymer film and process for manufacture thereof
US5338822A (en) * 1992-10-02 1994-08-16 Cargill, Incorporated Melt-stable lactide polymer composition and process for manufacture thereof
US5542594A (en) * 1993-10-06 1996-08-06 United States Surgical Corporation Surgical stapling apparatus with biocompatible surgical fabric
US6153231A (en) * 1997-06-25 2000-11-28 Wm. Wrigley Jr. Company Environmentally friendly chewing gum bases
US6608170B1 (en) * 1999-03-31 2003-08-19 Cornell Research Foundation, Inc. Syndiotactic poly(lactic acid)
US6325810B1 (en) 1999-06-30 2001-12-04 Ethicon, Inc. Foam buttress for stapling apparatus
US6273897B1 (en) 2000-02-29 2001-08-14 Ethicon, Inc. Surgical bettress and surgical stapling apparatus
US7959761B2 (en) * 2002-04-12 2011-06-14 Georgia-Pacific Consumer Products Lp Creping adhesive modifier and process for producing paper products
US8778375B2 (en) * 2005-04-29 2014-07-15 Advanced Cardiovascular Systems, Inc. Amorphous poly(D,L-lactide) coating
US8414584B2 (en) * 2008-07-09 2013-04-09 Icon Orthopaedic Concepts, Llc Ankle arthrodesis nail and outrigger assembly
US8328807B2 (en) * 2008-07-09 2012-12-11 Icon Orthopaedic Concepts, Llc Ankle arthrodesis nail and outrigger assembly
JP5748674B2 (ja) * 2009-03-13 2015-07-15 ネーチャーワークス エルエルシー メソラクチド流からの乳酸等価体の回収
EP2994462B2 (fr) * 2013-05-06 2019-08-21 Futerro S.A. Procede pour recuperer et ameliorer la production du meso-lactide a partir d'un flux contenant du lactide brut
US10202489B2 (en) 2017-03-08 2019-02-12 International Business Machines Corporation Lactide copolymers and ring-opened lactide copolymers
US10570252B2 (en) 2017-03-08 2020-02-25 International Business Machines Corporation Flame retardant lactide monomors for polylactide synthesis
CN106995429B (zh) * 2017-05-22 2019-06-04 浙江海正生物材料股份有限公司 一种内消旋丙交酯的分离方法
JP7638229B2 (ja) 2019-06-13 2025-03-03 ネイチャーワークス・エル・エル・シー 急速加水分解ポリラクチド樹脂組成物
CN114653086B (zh) * 2022-03-11 2025-02-11 孝感市易生新材料有限公司 一种制备高纯度l-丙交酯的装置及方法
CN115260459A (zh) * 2022-09-02 2022-11-01 浙江海正生物材料股份有限公司 一种聚乳酸-乙醇酸共聚物及其制备方法
WO2024160884A1 (fr) * 2023-02-01 2024-08-08 Totalenergies Corbion Bv Procédé de production d'un polyméso-lactide

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EP0427185A3 (en) * 1989-11-09 1992-04-15 Boehringer Ingelheim Kg Copolymers from trimethylenecarbonate and optically inactive lactides
EP0427185A2 (fr) * 1989-11-09 1991-05-15 Boehringer Ingelheim Kg Copolymères de carbonate de triméthylène et de lactides optiquement inactives
EP0893462A3 (fr) * 1992-01-24 1999-10-20 Cargill, Incorporated Procédé continu pour la préparation de lactide et polylactides
WO1994008078A1 (fr) * 1992-10-02 1994-04-14 Cargill, Incorporated Tissus de lactide polymere stables en fusion et procede de fabrication
EP0592911A1 (fr) * 1992-10-14 1994-04-20 BASF Aktiengesellschaft Procédé pour la fabrication par injection et moussage d'objets en polylactide à haute résistance et haute rigidité
EP1247808A3 (fr) * 1993-10-07 2003-03-19 Cargill, Incorporated Procédé continu pour la préparation de lactide et polylactide
EP1247808A2 (fr) * 1993-10-07 2002-10-09 Cargill, Incorporated Procédé continu pour la préparation de lactide et polylactide
WO1995009879A1 (fr) * 1993-10-07 1995-04-13 Cargill, Incorporated Procede pour la production continue de lactide et de polymeres de lactide
WO1998007458A1 (fr) * 1996-08-19 1998-02-26 Korea Institute Of Science And Technology Methode de revetement de surfaces destinees aux implants metalliques
WO2010022966A2 (fr) * 2008-08-29 2010-03-04 Uhde Inventa-Fischer Gmbh Procédé servant à préparer un mélange de dérivés de lactide
WO2010022966A3 (fr) * 2008-08-29 2010-06-24 Uhde Inventa-Fischer Gmbh Procédé servant à préparer un mélange de dérivés de lactide
US8957229B2 (en) 2008-08-29 2015-02-17 Uhde Inventa-Fischer Gmbh Method for the production of a mixture of lactide derivatives
DE102013011399A1 (de) 2012-07-31 2014-02-06 Amw Gmbh Implantat mit Risperidon
EP2876124A1 (fr) 2013-11-20 2015-05-27 Uhde Inventa-Fischer GmbH Procédé et dispositif de fabrication d'un mélange d'acide polylactique et mélange d'acide polylactique
WO2015074827A1 (fr) 2013-11-20 2015-05-28 Uhde Inventa-Fischer Gmbh Procédé et dispositif de production d'un mélange d'acides polylactique cristallisable et mélange d'acides polylactiques
US10414917B2 (en) 2013-11-20 2019-09-17 Uhde Inventa-Fischer Gmbh Process and apparatus for preparation of a crystallizable polylactic acid mixture, and polylactic acid mixture

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EP0318567A1 (fr) 1989-06-07
DE3869343T (fr) 1992-04-23
JPH02500593A (ja) 1990-03-01
DE3869343D1 (de) 1992-04-23
EP0318567B1 (fr) 1992-03-18
US4983745A (en) 1991-01-08

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